Determination of the concentration of a highly reactive intermediate of saccharides utilizing the reaction kinetics of the blue bottle reaction

Iain A. Smellie; Chao Dun Tan; Iain L.J. Patterson; Georg Hähner

doi:10.1007/s11144-025-02887-z

Determination of the concentration of a highly reactive intermediate of saccharides utilizing the reaction kinetics of the blue bottle reaction

Iain A. Smellie, Chao Dun Tan, Iain L.J. Patterson, Georg Hähner^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

In the present study we investigated fructose, glucose, and mannose in sodium hydroxide solution. Saccharides in an alkaline solution establish a highly reactive enediolate anion of low concentration. We propose that an internal geometric rearrangement of the sugar required to establish the enediolate is responsible for different concentrations of the reactive anion depending on the sugar. We determined the free energy for the rearrangement and the concentration of the enediolate. We find that for the sugars studied there is a correlation between the magnitude of internal rotation required for hydrogen abstraction and the value of the free energy.

Original language	English
Number of pages	16
Journal	Reaction Kinetics, Mechanisms and Catalysis
Volume	Online first
Early online date	23 Jun 2025
DOIs	https://doi.org/10.1007/s11144-025-02887-z
Publication status	E-pub ahead of print - 23 Jun 2025

Keywords

Saccharides
Reaction kinetics
Kinetic modelling
Intramolecular rearrangement
Enediolate concentration
Free energy

Access to Document

10.1007/s11144-025-02887-zLicence: CC BY

Smellie_2025_RKMaC_Determination-concentration-saccharides-blue-bottle-reaction_CC
© The Author(s) 2025. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence (https://creativecommons.org/licenses/by/4.0/), and indicate if changes were made.
Final published version, 1.45 MBLicence: CC BY

Determination of the Concentration of a Highly Reactive Intermediate of Saccharides Utilizing the Reaction Kinetics of the Blue Bottle Reaction (dataset)
Haehner, G. (Creator), Smellie, I. (Creator), Tan, C. D. (Creator) & Patterson, I. (Creator), University of St Andrews, 24 Jun 2025
DOI: 10.17630/c3fc51b9-16d8-4416-95ee-a7fee9183e98
Dataset

File

Cite this

@article{ae0652b52acb46459f264d0252725a5d,

title = "Determination of the concentration of a highly reactive intermediate of saccharides utilizing the reaction kinetics of the blue bottle reaction",

abstract = "In the present study we investigated fructose, glucose, and mannose in sodium hydroxide solution. Saccharides in an alkaline solution establish a highly reactive enediolate anion of low concentration. We propose that an internal geometric rearrangement of the sugar required to establish the enediolate is responsible for different concentrations of the reactive anion depending on the sugar. We determined the free energy for the rearrangement and the concentration of the enediolate. We find that for the sugars studied there is a correlation between the magnitude of internal rotation required for hydrogen abstraction and the value of the free energy.",

keywords = "Saccharides, Reaction kinetics, Kinetic modelling, Intramolecular rearrangement, Enediolate concentration, Free energy",

author = "Smellie, {Iain A.} and Tan, {Chao Dun} and Patterson, {Iain L.J.} and Georg H{\"a}hner",

note = "Funding: Financial support from the University of St. Andrews under a St Leonard{\textquoteright}s College Scholarship (CDT) is gratefully acknowledged. ",

year = "2025",

month = jun,

day = "23",

doi = "10.1007/s11144-025-02887-z",

language = "English",

volume = "Online first",

journal = "Reaction Kinetics, Mechanisms and Catalysis",

issn = "1878-5190",

publisher = "Springer Nature",

}

TY - JOUR

T1 - Determination of the concentration of a highly reactive intermediate of saccharides utilizing the reaction kinetics of the blue bottle reaction

AU - Smellie, Iain A.

AU - Tan, Chao Dun

AU - Patterson, Iain L.J.

AU - Hähner, Georg

N1 - Funding: Financial support from the University of St. Andrews under a St Leonard’s College Scholarship (CDT) is gratefully acknowledged.

PY - 2025/6/23

Y1 - 2025/6/23

N2 - In the present study we investigated fructose, glucose, and mannose in sodium hydroxide solution. Saccharides in an alkaline solution establish a highly reactive enediolate anion of low concentration. We propose that an internal geometric rearrangement of the sugar required to establish the enediolate is responsible for different concentrations of the reactive anion depending on the sugar. We determined the free energy for the rearrangement and the concentration of the enediolate. We find that for the sugars studied there is a correlation between the magnitude of internal rotation required for hydrogen abstraction and the value of the free energy.

AB - In the present study we investigated fructose, glucose, and mannose in sodium hydroxide solution. Saccharides in an alkaline solution establish a highly reactive enediolate anion of low concentration. We propose that an internal geometric rearrangement of the sugar required to establish the enediolate is responsible for different concentrations of the reactive anion depending on the sugar. We determined the free energy for the rearrangement and the concentration of the enediolate. We find that for the sugars studied there is a correlation between the magnitude of internal rotation required for hydrogen abstraction and the value of the free energy.

KW - Saccharides

KW - Reaction kinetics

KW - Kinetic modelling

KW - Intramolecular rearrangement

KW - Enediolate concentration

KW - Free energy

U2 - 10.1007/s11144-025-02887-z

DO - 10.1007/s11144-025-02887-z

M3 - Article

AN - SCOPUS:105008809704

SN - 1878-5190

VL - Online first

JO - Reaction Kinetics, Mechanisms and Catalysis

JF - Reaction Kinetics, Mechanisms and Catalysis

ER -

Determination of the concentration of a highly reactive intermediate of saccharides utilizing the reaction kinetics of the blue bottle reaction

Abstract

Keywords

Access to Document

Fingerprint

Datasets

Determination of the Concentration of a Highly Reactive Intermediate of Saccharides Utilizing the Reaction Kinetics of the Blue Bottle Reaction (dataset)

Cite this